TWI754154B - Post chemical mechanical planarization (cmp) cleaning - Google Patents

Abstract

Provided are formulations that offer a high cleaning effect on inorganic particles, organic residues, chemical residues, reaction products on the surface due to interaction of the wafer surface with the Chemical Mechanical Planarization (CMP) slurry and elevated levels of undesirable metals on the surface left on the semiconductor devices after the CMP. The post-CMP cleaning formulations comprise one or more organic acid, one or more polymer and a fluoride compound with pH >7 and optionally a surfactant with two sulfonic acid groups.

Description

Cleaning after chemical mechanical planarization (CMP)

Cross-referencing of related applications This application claims the benefit of US Provisional Application No. 62/690,108, filed June 26, 2018.

Field of Invention The present invention provides post-CMP cleaning formulations.

Among the steps involved in the manufacture of semiconductor devices, cleaning is required at individual steps to remove organic/inorganic residues. Cleaning methods to improve residue removal required in semiconductor manufacturing processes include: post-CMP (chemical mechanical planarization) cleaning, photoresist ash residue removal, photoresist removal, individual applications in back-end packaging such as pre-probe wafers Cleaning, cutting, grinding, etc.

There is a particular need for improved cleaning in post-CMP cleaning of individual structures formed by chemical mechanical planarization (CMP) processes. The CMP process involves polishing one or more films deposited on a wafer by pressing the wafer against a polishing pad with a CMP slurry to provide abrasive removal of material and provide planarity.

After the CMP step, the wafer surface contains numerous defects that, if not removed from the surface, would result in a defective wafer as the final product. Typical defects after the CMP process are inorganic particles, organic residues, chemical residues, reaction products on the wafer surface due to interaction of the wafer surface with the CMP slurry, and elevated amounts of unwanted metals on the surface. After the polishing step, the wafer is cleaned, most commonly using a brush scrubbing process. During this process, cleaning chemicals are dispensed onto the wafer to clean the wafer. The wafer was additionally rinsed with deionized (DI) water prior to the drying process.

Previous works completed in the field of this case include: JP 11-181494; US Patent No. 6,440,856; US Patent No. 7,497,966 B2; US Patent No. 7,427,362 B2; US Patent No. 7,163,644 B2; US Patent No. 7,396,806; US Patent No. 6,730,644; US Patent No. 7,084,097; US Patent No. 6,147,002; US 2003/0129078; and US 2005/0067164.

As technology advances, threshold dimensions and defect counts, which are critical to the throughput of semiconductor wafers, become smaller, increasing the performance requirements of post-CMP cleaners. Advanced semiconductor devices containing tungsten interconnects pose particular challenges due to metal residues that can cause electrical degradation. The root cause of metal residues is often the iron compound used in the polishing slurry and the precipitation of the titanium compound due to the removal of the titanium-based barrier layer during this polishing step. Therefore, it is critical to the cleaning formulation to remove these metal residues in order to provide the desired electrical performance for the semiconductor device. The formulations or compositions of the present invention (formulations and compositions are interchangeable) have been found to be very effective in removing residues left by the CMP polishing process described above.

Described herein are post-CMP cleaning compositions, methods and systems for post-CMP processing.

In one aspect, the present invention provides a cleaning composition comprising: water; at least one organic acid or a salt thereof, a fluoride, a polymer additive and optionally a surfactant, a corrosion inhibitor, an antifoam, Biological preservatives, pH adjusters.

The polymer additive may be selected from the group consisting of anionic, cationic and nonionic polymers or copolymers. The polymer additive may be selected from, but not limited to, acrylic acid-acrylamidopropane sulfonic acid copolymer, poly(acrylic acid), poly(methacrylic acid), poly(2-acrylamido-2-methyl- 1-propanesulfonic acid), carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, poly(1-vinylpyrrolidone-2-dimethylaminoethyl methacrylate) copolymer, poly (sodium 4-styrene sulfonate), poly(ethylene oxide), poly(4-styrene sulfonic acid), polyacrylamide, poly(acrylamide/acrylic acid) copolymer and combinations thereof and salts thereof group.

In a preferred embodiment, the formulation includes an anionic polymer. The preferred anionic polymer is acrylic acid-acrylamidopropane sulfonic acid copolymer.

Another preferred polymer/copolymer is a nonionic polymer containing ethylene oxide (EO) groups.

The at least one organic acid or its salt can preferably be selected from the group consisting of dicarboxylic acid or its salt, hydroxycarboxylic acid or its salt, and polycarboxylic acid or its salt. Preferred organic acids or salts thereof are oxalic acid and citric acid or salts thereof. The concentration of organic acid or salt thereof in the formulation may be 1 to 30% by weight, or more preferably between 5 and 20%, wherein the composition is diluted 2 to 500 times with water at the point of use.

The formula also contains fluoride. Examples of fluorides include hydrofluoric acid, ammonium fluoride, ammonium bifluoride, quaternary ammonium fluoride. The preferred compound is ammonium fluoride. The concentration of the fluoride component in the formulation is in the range of 1 to 25 wt %, or between 2 to 20 wt %, 3 to 18 wt %, or between 4 and 10 wt %, wherein the formulation Dilute 2 to 500 times at point of use.

In another preferred embodiment, the cleaning composition comprises 1 to 15% by weight of organic acid or its salt, 0.05 to 3% by weight of polymer/copolymer, 1 to 25% by weight of fluoride, water, wherein the The composition can be diluted 2 to 500 times with deionized water at the point of use.

In another preferred embodiment, the cleaning composition comprises 1 to 30% by weight of organic acid or its salt, 0.05 to 3% by weight of polymer, 1 to 25% by weight of fluoride, water, wherein the composition It can be diluted 2 to 500 times at the point of use with DI water, and the polymer is selected from the group consisting of anionic polymers/copolymers and nonionic polymers/copolymers containing ethylene oxide (EO) groups.

In another preferred embodiment, the cleaning composition comprises 1 to 30% by weight of organic acid or its salt, 0.05 to 3% by weight of polymer/copolymer, 1 to 25% by weight of fluoride, water, wherein The composition can be diluted 2 to 500 times with DI water at the point of use, and the at least one polymer is an anionic polymer/copolymer and a nonionic polymer/copolymer comprising ethylene oxide (EO) groups.

In another preferred embodiment, the cleaning composition comprises 1 to 30% by weight of organic acid or its salt, 0.05 to 3% by weight of polymer/copolymer, 1 to 25% by weight of fluoride, water, wherein The composition can be diluted 2 to 500 times with DI water at the point of use, and the polymer is selected from acrylic acid-acrylamidopropane sulfonic acid copolymers and nonionic polymers containing ethylene oxide (EO) groups/ A group of copolymers.

In another preferred embodiment, the cleaning composition comprises 1 to 30% by weight of organic acid or its salt, 0.05 to 3% by weight of polymer mixture, 1 to 25% by weight of fluoride, water, wherein the combination The compound can be diluted 2 to 500 times with DI water at the point of use, and at least one copolymer is an acrylic acid-acrylamido propane sulfonic acid copolymer and another nonionic polymer/copolymer containing ethylene oxide (EO) groups thing.

In another preferred embodiment, the formulation comprises 0.5 to 5% by weight of oxalic acid, 0.5 to 5% by weight of citric acid or its salt, 0.5 to 5% by weight of malonic acid or its salt, 0.1 to 2% by weight Acrylic acid-acrylamidopropane sulfonic acid copolymer, 1 to 25 wt% fluoride and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the formulation comprises 0.5 to 5% by weight of oxalic acid, 0.5 to 5% by weight of citric acid or a salt thereof, 0.5 to 5% by weight of malonic acid, 0.1 to 3% by weight of a A nonionic polymer or copolymer of an oxyethane group, 1 to 25% by weight of a fluorine compound and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the formulation comprises 0.5 to 5 wt % of oxalic acid, 0.5 to 5 wt % of citric acid, 0.5 to 5 wt % of malonic acid or its salt, 0.1 to 3 wt % of a Nonionic polymer or copolymer of oxyethane group, 0.1 to 2 wt% anionic polymer, 1 to 25 wt% fluorine compound and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use .

In another preferred embodiment, the formulation comprises 1 to 30% by weight of citric acid or its salt, 0.1 to 3% by weight of acrylic acid-acrylamidopropane sulfonic acid copolymer, 1 to 25% by weight of fluorine compound and water, where the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the formulation comprises 1 to 30% by weight of citric acid or a salt thereof, 0.1 to 3% by weight of a nonionic polymer or copolymer containing an ethylene oxide group, 1 to 25% by weight of fluorochemicals and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the formulation comprises 1 to 30% by weight of citric acid or a salt thereof, 0.1 to 3% by weight of a nonionic polymer or copolymer containing an ethylene oxide group, and 0.1 to 3% by weight of anionic polymer, 1 to 25 wt% fluoride and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the formulation comprises 1 to 30% by weight of citric acid, 0.1 to 5% by weight of oxalic acid or a salt thereof, 0.1 to 3% by weight of acrylic acid-acrylamidopropanesulfonic acid copolymer and Water; wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the formulation comprises 1 to 30% by weight of organic acid or its salt, 0.1 to 3% by weight of polymer, 1 to 25% by weight of fluoride, 0.01 to 3% by weight of surface activity agent and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the cleaning composition comprises 1 to 30% by weight of organic acid or its salt, 0.1 to 3% by weight of polymer, 1 to 25% by weight of fluoride, 0.01 to 3% by weight of A surfactant comprising a di-negatively charged anionic group and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

In another preferred embodiment, the cleaning composition comprises 1 to 30% by weight of organic acid or its salt, 0.1 to 3% by weight of polymer, 1 to 25% by weight of fluoride, 0.01 to 3% by weight of Diphenyldisulfonic acid surfactant and water, wherein the composition can be diluted 2 to 500 times with DI water at the point of use.

The pH of the formulation is preferably between 1 and 7, or more preferably between 3 and 6, or more preferably between 4 and 5, wherein the formulation is diluted 2 with DI water at the point of use to 500 times.

The compositions of the present invention can be used to clean semiconductor wafers comprising at least one or more metal or dielectric films on the surface. The metal film may include interconnecting metal lines or vias comprising copper, tungsten, cobalt, aluminum, ruthenium, or alloys thereof. The dielectric layer may be a silicon oxide film such as one derived from a tetraethylorthosilicate (TEOS) precursor, a dielectric film having one or more elements such as silicon, carbon, nitrogen, oxygen, and hydrogen. The dielectric film may be porous or non-porous, or the structure may contain air gaps.

Cleaning compositions The wafer surface can be cleaned using various types of cleaning techniques including, but not limited to, brush box cleaning, spray cleaning, ultrasonic cleaning, buff cleaning on a pad, single Wafer spray tools, batch immersion cleaning tools, and more.

In some preferred embodiments, when the cleaning composition is diluted with water, it can be preferably between 0.2 and 50 angstroms/min, or more preferably between 1 and 20 angstroms/min, or most The dielectric film is etched at an etch rate preferably between 1 and 10 Angstroms/minute.

In certain preferred embodiments, the cleaning composition etches dielectric films at etch rates of 1 to 10 angstroms/min when diluted with water, and etches tungsten at etch rates of less than 1 angstroms/min, and when nitriding When the etching time of the titanium film is 5 minutes or less, the titanium nitride film is etched at an etching rate of less than 5 angstroms/min at room temperature.

In another aspect, the present invention is a post-CMP cleaning method of a semiconductor wafer comprising at least one or more metal or/and dielectric films, comprising provide the semiconductor wafer; providing the above post-CMP cleaning composition; and The semiconductor wafer is cleaned using the post-CMP cleaning composition.

In another aspect, the present invention is a post-CMP cleaning system for a semiconductor wafer comprising at least one or more metal or/and dielectric films comprising the semiconductor wafer; The above post-CMP cleaning composition; At least a portion of the metal or dielectric film therein is in contact with the post-CMP cleaning composition.

Described and disclosed herein are compositions for cleaning in semiconductor fabrication, including post chemical mechanical planarization (CMP) cleaning, photoresist ash residue removal, photoresist removal, various applications in back end packaging such as preprobing Needle wafer cleaning, dicing, grinding, etc. This formula works best as a post-CMP cleaning formula.

The formulations of the present invention are particularly suitable for post-CMP cleaning formulations following CMP processes including metal CMP processes, wherein the CMP processes result in the formation of metal interconnect structures surrounded by dielectrics; and dielectric CMP processes, Wherein one or more dielectrics are polished to form a flat surface or structure. Examples of metal CMP processes include, but are not limited to, tungsten CMP, copper CMP, cobalt CMP, ruthenium CMP, aluminum CMP, in which metal lines or vias are formed separated by dielectric regions. Examples of dielectric CMP include shallow trench isolation (STI) CMP, in which silicon oxide structures are formed separated by silicon nitride regions and interlayer dielectric (ILD) polishing.

The formulations of the present invention can effectively clean substrates after polishing with slurries of various types of particles, including but not limited to colloidal silica, surface charge modified silica particles (positively and negatively charged), Fumed silica, ceria (calcined and colloidal), alumina, zirconia, composite particles comprising two or more different types of particles.

In a preferred embodiment, the cleaning formulation of the present invention is used for post-CMP cleaning after tungsten CMP. The formulations of the present invention are particularly effective for removal of metal residues such as Fe, W, Ti and TiN, which are typically formed on the wafer surface after tungsten CMP, while significantly improving organic and inorganic residue removal capabilities. The formulations of the present invention are suitable for reducing tungsten corrosion, reducing surface roughness and reducing galvanic corrosion between tungsten and the lining material.

The cleaning chemistry comprises at least one organic acid or salt thereof, fluoride, polymer additives, water and optionally surfactants, corrosion inhibitors, biological preservatives, antifoams, pH adjusters.

Organic acids or mixtures thereof: Organic acids or salts thereof may be selected from a wide range of acids or salts thereof, such as monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, hydroxycarboxylic acids or mixtures thereof. Specific examples of organic acids include, but are not limited to: oxalic acid, citric acid, maleic acid, malic acid, malonic acid, gluconic acid, glutaric acid, ascorbic acid, formic acid, acetic acid, ethylenediaminetetraacetic acid, diethylenetriacetic acid Amine pentaacetic acid, glycine, alpha-alanine, cystine, etc. Salts of these acids can also be used. Acid/salt mixtures can also be used. The role of organic acids is to improve trace metal removal, remove organic residues, adjust pH or reduce metal corrosion. In a preferred embodiment, the formulation includes at least one hydroxycarboxylic acid. Examples of hydroxycarboxylic acids include, but are not limited to, citric acid, gluconic acid, lactic acid, glycolic acid, tartaric acid, mandelic acid, malic acid, and salicylic acid. Hydroxycarboxylic acids were found to be particularly suitable for removing titanium-related residues from the wafer surface. In some preferred embodiments, the cleaning formulation also includes a dicarboxylic acid effective to remove iron-related compounds from the wafer surface. Examples of dicarboxylic acids include, but are not limited to, oxalic acid, malonic acid, succinic acid, and glutaric acid. In one embodiment, the cleaning composition includes one or more organic acids selected from the group consisting of oxalic acid, citric acid, malonic acid, glycine, and alpha-alanine. In another embodiment of the cleaning composition, the organic acid comprises a mixture of oxalic acid, citric acid and malonic acid. In another preferred embodiment, the organic acid contains citric acid. In another specific example, the organic acid comprises a mixture of citric acid and oxalic acid.

The cleaning chemistry may contain from 1% to 30% by weight or more preferably between 5% and 20% by weight of at least one organic acid/salt.

Cleaning formulations may contain water soluble polymer additives. The polymers can be homopolymers or copolymers. The polymers may contain positively charged species (cationic polymers), negatively charged groups (anionic polymers), nonionic groups (nonionic polymers), or cationic and anionic groups (zwitterionic polymers (zwitterionic polymers) polymers)). The polymer may be selected from, but not limited to, acrylic acid-acrylamidopropane sulfonic acid copolymer, poly(acrylic acid), poly(methacrylic acid), poly(2-acrylamido-2-methyl-1- propanesulfonic acid), carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, poly(1-vinylpyrrolidone-2-dimethylaminoethyl methacrylate) copolymer, poly(4 - sodium styrene sulfonate), poly(ethylene oxide) or poly(ethylene glycol), poly(4-polyethylene sulfonic acid), polypropylene amide, poly(acrylamide/acrylic acid) copolymer, poly The group of vinyl alcohol and combinations thereof, and salts thereof. The molecular weight of the polymer may range from 100 to 10,000,000. Molecular weight can be measured by any suitable technique such as gel permeation chromatography (GPC), mass spectrometry (MALDI TOF-MS) and light scattering.

In some embodiments, the formulation includes one or more anionic polymers or copolymers. A preferred anionic polymer is acrylic acid-acrylamidopropane sulfonic acid copolymer (AA-AMPS). In preferred embodiments, the molecular weight of the polymer may be between 100 and 1,000,000, or more preferably between 200 and 100,000, or most preferably between 1000 and 10,000. In some more preferred embodiments, the molar ratio (x:y) of acrylic acid (x):2-acrylamido-2-methylpropanesulfonic acid (y) in the copolymer is 90:10 between 70:30.

An example of a preferred AA-AMPS copolymer used in the working examples is Dequest® P9300 available from Italmatch Chemicals (Genova, Italy).

In some other embodiments, the formulation includes one or more polymers or copolymers that are nonionic in nature and contain ethylene oxide (EO) groups. Examples of such polymers or copolymers include polyethylene glycol or various configurations of ethylene oxide (EO) based and polypropylene oxide (PO) based copolymers such as EO-PO-EO or PO-EO-PO . The molecular weight range is between 100 and 1,000,000, or more preferably between 200 and 100,000 or most preferably between 200 and 50,000.

In some preferred embodiments, the formulation includes an anionic polymer/copolymer and an ethylene oxide group-containing nonionic polymer/copolymer.

The addition of this polymer to a post-CMP formulation with an appropriate base resulted in a substantial improvement in cleaning performance. Without being combined with any particular mechanism, one of the possible mechanisms could be physical adsorption on the surface, which would prevent redeposition of removed particles and other residues. Another possible mechanism is a strong affinity for this residue (organic), thereby enhancing the driving force for stripping during the cleaning process. Nonionic polymer additives containing EO groups can form bonds with the hydrated silica surface and form a polymer coating that aids in particle removal.

These types of polymers or mixtures thereof can be added to the cleaning formulation at a concentration of 0.01 to 10% by weight. The preferred concentration range is from 0.1% to 5% by weight. The formulation can be diluted 2 to 500 times at the point of use by adding a solvent such as water. Alternatively, the formulation can be supplied in diluted form for immediate use without dilution at the point of use.

Fluoride is also included in the formula. Examples of fluorides include hydrofluoric acid, ammonium fluoride, ammonium bifluoride, quaternary ammonium fluoride. The preferred compound is ammonium fluoride. The concentration of the fluoride component in the formulation is preferably in the range of 1 to 25% by weight, or more preferably between 3 and 20% by weight or most preferably between 4 and 18% by weight, wherein The formulation is diluted 2 to 500 times at the point of use. At acidic pH, the fluoride species may dissociate and different types of fluoride ions may be formed. For example, an acidic formulation with a fluoride salt such as ammonium fluoride can have three different species present together: hydrofluoric acid (HF), fluoride ion (F ⁻ ), and difluoride ion (HF ²⁻ ).

The pH of the formulation is preferably between 1 and 7, or more preferably between 3 and 6 or most preferably between 4 and 5, wherein the formulation is diluted 2 with DI water at the point of use to 500 times.

In certain embodiments, the difference between the total equivalents of organic acids and the molar concentration of fluoride in the formulation is between -2 and 2 or more preferably between 0 and 2. If the difference is less than -2, the etch rates of the TEOS and SiN dielectrics will be too low to effectively clean the dielectrics. If the difference is greater than 2, the dielectric loss during the cleaning process may be unacceptably high.

With regard to post-CMP cleaning formulations, there may be additional components that contribute to cleaning performance. Common types of additives include the following.

Surfactants: Surfactants are used in cleaning chemicals to improve the wettability of the surface being cleaned and to assist in removing residues from the surface without redepositing on the surface. The addition of surfactants also reduces the surface tension of the solution, preferably 10 dynes/cm, or more preferably 20 dynes/cm, or optimally 30 dynes/cm. The surface tension of the post-CMP solution containing the surfactant when diluted 50 times with water is preferably between 15 and 75 dynes/cm, or more preferably between 20 and 60 dynes/cm, or most preferably between 15 and 75 dynes/cm. between 20 and 50 dynes/cm. Surfactants can also reduce water marks on the surface, which are associated with defects formed during the drying phase following cleaning. Any type of surfactant anionic/cationic/nonionic/zwitterionic or combination thereof can be used. The selection of this surfactant can depend on various criteria including: wetting, foaming, cleaning power, rinsability, and the like. Combinations of surfactants can also be used in which one surfactant is used to dissolve the less soluble hydrophobic surfactant molecules.

The compositions of the present invention optionally contain surfactants, which in part help protect the wafer surface during and after polishing to reduce defects in the wafer surface. Surfactants can also be used to control the removal rate of some films used in polishing, such as low-k dielectrics. Suitable surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.

Nonionic surfactants can be selected from a range of chemical types including, but not limited to, long chain alcohols, ethoxylated alcohols, ethoxylated acetylene glycol surfactants, polyethylene glycol alkyl ethers, propylene glycol alkanes base ether, glucoside alkyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol alkyl pentadienyl ether, glycerol alkyl ester, polyoxyethylene glycol sorbitol alkyl ester, sorbose Alkyl alcohol esters, cocoamide monoethanolamine, cocoamide diethanolamine dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, fluorine-containing Surfactant. The molecular weight of the surfactant can range from a few hundred to over a million. The viscosity of these materials also has a very broad distribution.

Anionic surfactants include, but are not limited to, salts with suitable hydrophobic tails such as alkyl carboxylates, alkyl polyacrylates, alkyl sulfates, alkyl phosphates, alkyl dicarboxylates, alkyl sulfates Hydrogen salts, alkyl hydrogen phosphates, such as alkoxy carboxylates, alkoxy sulfates, alkoxy phosphates, alkoxy dicarboxylates, alkoxy hydrogen sulfates, alkoxy hydrogen phosphates , such as substituted aryl carboxylates, substituted aryl sulfates, substituted aryl phosphates, substituted aryl dicarboxylates, substituted aryl hydrogen sulfates, and substituted aryl bisulfates base hydrogen phosphate, etc. Counter ions of such surfactants include, but are not limited to, potassium, ammonium, and other positive ions. The molecular weights of these anionic surface wetting agents range from hundreds to hundreds of thousands.

Cationic surfactants have a positive net charge on the majority of the molecular backbone. Cationic surfactants are typically halides of molecules containing hydrophobic chains and cationic charge centers such as amine, quaternary ammonium, benzalkonium, and alkylpyridinium ions.

In another aspect, the surfactant can be an amphoteric surfactant having positive (cationic) and negative (anionic) charges and their associated counterions on the main molecular chain. The cationic moiety is dominated by primary, secondary or tertiary amine or quaternary ammonium cations. The anionic moiety may vary more and includes sulfonates like CHAPS (3-[(3-cholamidopropyl)-diethylamine]-propanesulfonic acid) and cocoamide like the sulfobetaines The situation in propyl betaine. Betaines such as cocamidopropyl betaine have carboxylates with ammonium. Some amphoteric surfactants may have phosphate anions with amines or ammonium, such as phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins of phospholipids ).

Examples of surfactants also include, but are not limited to, sodium lauryl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, second alkanesulfonates, alcohol ethoxylates, acetylene-based surfactants agents and any combination thereof. Examples of suitable commercially available surfactants include Hostapur® SAS-30 from Clariant Chemicals, TRITON™, Tergitol ^™ , DOWFAX ^™ surfactant series manufactured by Dow Chemicals, and SURFYNOL™, DYNOL ^™ , manufactured by Air Products and Chemicals, Various surfactants from the Zetasperse ^™ , Nonidet ^™ and Tomadol ^™ surfactant series. Suitable surfactants may also include polymers containing ethylene oxide (EO) groups and propylene oxide (PO) groups. An example of an EO-PO polymer is Tetronic™ 90R4 from BASF Chemicals.

In a preferred embodiment, the surfactant includes an ethoxylate group and a propyloxylate group.

In another embodiment, a surfactant is a linear molecule that can be represented by the following structure, wherein m is between 1 and 100 and n is between 0 and 100.

An example of a surfactant with this structure is Tergitol ^™ MinFoam Ix from Dow Chemicals.

Particularly useful surfactants in these formulations are those that remain stable in the presence of high ionic strength and fluoride species. Without any particular theory, at high ionic strengths, the repulsive forces between the two surfactant molecules are significantly reduced, causing the molecules to approach each other, thereby making the solution cloudy or cloudy. This cloudy solution may be unacceptable in advanced semiconductor manufacturing because particle count measurements in this solution will have unacceptably high values. High ionic strength is the result of high concentrations of additives with ionizable groups. The ionic strength can be determined by conducting conductivity measurements at 25°C. Preferably the surfactant should be stable in solution without any turbidity or precipitation at a concentration of at least 0.1 wt% in solutions with a conductivity of at least 40 mS/cm. Ideally it may be that the surfactant should be stable in solutions of even higher conductivity such as 60 mS/cm or 80 mS/cm.

We want the surfactant to have more than two anionic groups. Surfactants with di or more anionic groups may have sufficient electrostatic fields even in highly ionic solutions. Therefore the surfactant solution will be stable. In some preferred embodiments, the surfactant has two or more sulfonic acid groups.

A preferred surfactant is diphenyl ether disulfonic acid or a salt thereof. The structure of the preferred surfactant is shown below:

wherein R is a group selected from H or a linear or branched alkyl group having a carbon chain length between 1 and 20.

Examples of surfactants having this structure include Dowfax 2A1, Dowfax 3B2, Calfax DBA70.

In another preferred embodiment, the surfactant is a fluorosurfactant. Examples of fluorosurfactants include, but are not limited to, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA), perfluorohexanoic acid (PFHxA), perfluorobutane sulfonic acid, or perfluorooctane sulfonic acid (PFOA). Fluorobutane sulfonate (PFBS).

The surfactant may be used at a concentration of 0.0001 to 10% by weight, or more preferably between 0.01% and 3% by weight and most preferably between 0.05% and 1% by weight.

The cleaning chemistry may optionally contain a chelating agent. Since chelating agents can be more selective for one metal ion than another, many chelating agents or salts thereof are used in the compositions described herein. It is believed that these chelating agents can bind to metal ion contaminants on the surface of the substrate and dissolve them in the composition. Furthermore, in certain embodiments, the chelating agent should retain the metal ions in the composition and prevent the ions from redepositing on the substrate surface. Examples of suitable chelating agents that can be used include, but are not limited to: ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid (NHEDTA), nitrile triacetic acid (NTA), diethylenetriamine Pentaacetic acid (DPTA), ethanol diglycine, citric acid, gluconic acid, oxalic acid, phosphoric acid, tartaric acid, methyldiphosphonic acid, aminotrimethylenephosphonic acid, ethylene-diphosphonic acid, 1-hydroxylidene Ethyl-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, ethylamino dimethylenephosphonic acid, dodecylamino dimethylenephosphonic acid, Nitrile trimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and 1,2-propane Diaminetetramethylenephosphonic acid or ammonium salt, organic amine salt, maronic acid, succinic acid, dimercaptosuccinic acid, glutaric acid, maleic acid, phthalic acid, fumaric acid, Polycarboxylic acids such as tricarboxylic acid, propane-1,1,2,3-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, 1,2,4,5-mellitic acid, hydroxy Oxycarboxylic acids such as glycolic acid, beta-hydroxypropionic acid, citric acid, malic acid, tartaric acid, pyruvic acid, diglycolic acid, salicylic acid, gallic acid, polyphenols such as catechol, pyrogallol, phosphoric acids such as pyrophosphoric acid, polyphosphoric acid, heterocyclic compounds such as 8-hydroxyquinoline and diketones such as alpha-dipyridylacetone acetone.

The chelating agent can be used at a concentration of from 0.01% to 30% by weight.

The cleaning chemistry may optionally contain an anti-foaming compound. The defoamer or anti-foaming agent is a chemical additive that reduces and hinders foam formation in the formulation. The terms defoamer and defoamer are often used interchangeably. Commonly used agents are insoluble oils, polydimethylsiloxanes and other polysiloxanes, certain alcohols, stearates and glycols, certain surfactants such as polyether surfactants and A combination of polyol fatty acid esters, Surfynol MD20 surfactant from Evonik Chemicals. The anti-foaming compound can be used in the cleaning formulation at a concentration of between 0.00001% to 0.01% by weight.

The cleaning chemistry may optionally contain a biocide. CMP formulations may also contain additives to control biological growth such as biocides. Some additives to control biological growth are disclosed in US Patent No. 5,230,833 (Romberger et al.) and US Patent Publication No. 2002/0025762, incorporated herein by reference. Biological growth inhibitors include, but are not limited to, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, alkylbenzyldimethylammonium chloride, and alkylphenyldimethylammonium hydroxide Ammonium (wherein the alkyl chain is from 1 to about 20 carbon atoms), sodium chlorite, sodium hypochlorite, isothiazolinone compounds such as methylisothiazolinone, methylchloroisothiazolinone, and benzisothiazole Linones. Some commercially available preservatives include the KATHON ^™ and NEOLENE ^™ product lines from Dow Chemicals and the Preventol™ line from Lanxess.

The preferred biocides are isothiazolinone compounds such as methylisothiazolinone, methylchloroisothiazolinone and benzisothiazolinone.

The CMP polishing composition optionally contains from 0.0001 wt% to 0.10 wt% biocide, preferably from 0.0001 wt% to 0.005 wt%, and more preferably from 0.0002 wt% to 0.0025 wt% to prevent bacteria during storage and fungal growth.

Chemicals containing this polymer can be used in a variety of cleaning applications that require residue removal from surfaces. The residue may be inorganic or organic in nature. Examples of processes where formulations containing these polymers may be effective include: post-CMP cleaning, photoresist ash residue removal, photoresist removal, and various applications in back-end packaging such as: pre-probe wafer cleaning, dicing, grinding, etc. etc. and cleaning of wafers for photovoltaic applications.

The compositions of the present invention are particularly useful for cleaning semiconductor wafers containing at least one or more metal or dielectric films on the surface. The metal film may include interconnecting metal lines or vias including copper, tungsten, cobalt, aluminum, ruthenium, titanium, germanium-antimony-tellurium (GST) or alloys thereof. The dielectric layer may be a silicon oxide film such as one derived from a tetraethylorthosilicate (TEOS) precursor, a dielectric film having one or more elements such as silicon, carbon, nitrogen, oxygen, and hydrogen. The dielectric film may be porous or non-porous, or the structure may contain air gaps.

Cleaning compositions The wafer surface can be cleaned using various types of cleaning techniques including, but not limited to, brush box cleaning, spray cleaning, ultrasonic cleaning, polishing on pad cleaning, single wafer spray tools, batch immersion cleaning tools, and the like .

In certain preferred embodiments, the cleaning composition can be preferably between 0.2 and 50 angstroms/min, or more preferably between 1 and 20 angstroms/min at room temperature when diluted with water The dielectric film is etched at an etch rate in between.

In some preferred embodiments, the room temperature etch rate of the metal films (tungsten and titanium nitride) is very low, preferably less than 10 angstroms/min, or more preferably less than 5 angstroms/min or most preferably less than 2 angstroms /Minute.

The formulations of the present invention are particularly suitable for post-CMP cleaning applications of tungsten. Tungsten CMP produces metallic residues including W, Ti, and Fe, which can form invisible residues on the dielectric surface. These residues can increase leakage current and reduce the effectiveness of the semiconductor device. Titanium is particularly difficult to remove from the wafer surface because titanium is generally stable in the solid oxide phase over a wide pH range. Due to suitable organic acids and dielectric etch capabilities, the formulations of the present invention can effectively remove titanium residues and improve the electrical performance of the device.

The formulation or components of the formulation can be purified and filtered when the formulation is manufactured or when the formulation is used. In some embodiments, the formulation can be made into two or more components and mixed at the point of use.

The cleaning compositions and methods described herein will be exemplified in more detail with reference to the following examples, but should not be construed to be limited thereto.

All post-CMP cleaning compositions used in the working examples had a pH between 4 and 5. Working Example Example 1

This example performed electrochemical tests to characterize the removal of Ti.

Table 1 provides passivation current densities for various chemistries tested at 0.2 wt% concentration. Table 1

At acidic pH, Ti exhibits passivation properties at anodic potential. The steady-state passivation current density is the result of a balance between oxide film formation and oxide film dissolution. Therefore, this steady-state passivation current density can be used as a proxy for the solution's ability to dissolve titanium residues.

An example of a polarization diagram is shown in Figure 1.

The data show that hydroxycarboxylic acids such as citric acid, gluconic acid, lactic acid show high passivation current densities, indicating a strong ability to complex with Ti compounds. Example 2

TEOS wafers were polished on Mirra® manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054. The wafer rested on platen 1 and was polished for 1 minute on an IC1000 pad from Dow Chemicals with a commercial tungsten block polishing slurry.

Cleaning was performed on an Ontrak cleaning machine using a second brush box and the cleaning schedule consisted of 30 seconds chemical dispensing and 20 seconds DI water rinse in the first brush box and 10 seconds chemical dispensing and 20 seconds in the second brush box station. 40 seconds DI water rinse. Table 2

The concentrated cleaning compositions described were prepared according to Table 2. The acid concentration was chosen to provide the same molar concentration. The remainder of the composition is water. These chemicals were further diluted with water and 40% ammonium fluoride in the proportions in Table 3.

To characterize defect removal and trace metal removal capabilities, the following test sequence was performed. For each formulation, 3 oxide replicas were polished, followed by conditioning 3 TEOS monitors using an ex-situ pad. The pads were then contaminated by polishing 3 TiN wafers without any pad conditioning. The TEOS wafer monitor was then inspected by vapor phase decomposition inductively coupled plasma mass spectrometry (VPD-ICPMS) to determine residual metal contamination on the surface.

The first three TEOS monitor wafers were analyzed using the Surfscan™ SP2 from KLA-Tencor with a sensitivity of 0.07 microns.

In addition, etch rates were measured on TEOS, Ti and W wafers at room temperature. table 3

The etch rate was measured at room temperature with stirring. The etching time for TEOS was 30 minutes. The etching time for the W and Ti films was 5 minutes. The TEOS etch rate was measured with ellipsometry, while the W and Ti etch rates were measured with the four-point probe technique.

Table 4 summarizes these data.

實施例 3 Table 4 shows that hydroxycarboxylic acids like citric acid (D6) provide better Ti removal. Dicarboxylic acids like oxalic acid (D5) are more suitable for Fe removal. Citric acid also provides excellent defectivity. By using ammonium fluoride, TEOS defects can be significantly reduced by increasing the TEOS etch rate. Table 4

Example 3

The following recipes were prepared as shown in Table 5. All formulations contain NH4F and water.

Dowfax 2A1, Dowfax 3B2, Calfax DBA70 and Calfax 10L-45 are patented surfactants containing diphenyldisulfonic acid structure with alkyl groups.

Hostapur SAS is a secondary alkanesulfonic acid surfactant containing only one sulfonic acid group. Tergitol Minfoam 1x is a nonionic surfactant. table 5

The data in Table 5 shows that formulations C6 and C7 were cloudy, while C8 to C10 were clear. The conductivity of all solutions measured at 250°C was about 90 mS/cm.

Thus, it is clear that surfactants with disulfonic acid groups are stable in formulations with very high electrical conductivity (about 90 mS/cm). Example 4

The formulations were made with various additives (polymers and surfactants) in an alkaline chemistry comprising 13.79 wt% citric acid and 5 wt% ammonium fluoride, the balance being water. This formula is diluted with 1 part formula in 49 parts water. Additives were then added to the diluted formulation as described in Table 6 at a concentration of 0.2% by weight.

For cleaning evaluation, a polished tungsten wafer was first contaminated by immersion in a 3 wt% colloidal silica (Fuso PL-3 Particles) slurry at pH 2.3 for 30 minutes, resulting in a nearly complete particle-covered tungsten surface . The wafers were then cleaned by immersion in the cleaning solution for 5 minutes with agitation. The particle cleaning effect was assessed by scanning electron microscopy at 10,000x magnification. Cleaning performance was subjectively classified as excellent (grain area coverage after cleaning > 10% of the imaged area), moderate (grain area coverage after cleaning 10 to 50% of the imaged area), and poor (grain area after cleaning area coverage over 50%). Table 6

It is evident from this table that additives containing only polyethylene glycol groups such as polyethylene glycol (molecular weight 400, 1000, 4000, 12000), copolymers of polyethylene glycol (PEO) and polypropylene glycol (PPO) such as Pluronic Those formulations of L64 and Pluronic 17R4 provide excellent cleaning performance. Example 5

TEOS and SiN wafers were polished with tungsten polish slurry and cleaned using IC1000 pads on a Mirra polisher. The concentrate formulations used are summarized in Table 7. The formula is diluted with 1 part formula in 49 parts water to make a point-of-use cleaning formula. The wafers were cleaned with these recipes on an Ontrak DSS200 cleaner. Cleaning was performed on an Ontrak cleaning machine using a second brush box, and the cleaning schedule consisted of 30 seconds of chemical dispensing and 320 seconds of DI water rinse in the first brush box and 10 seconds of chemical dispensing in the second brush box station and 40 seconds DI water rinse.

Table 7 also summarizes the number of defects measured on TEOS and SiN wafers using the KLA Surfscan SP2 defect metrology tool.

In addition, tungsten cleaning was performed using the method described in Example 4. The ability to clean silicon oxide particles from tungsten surfaces is also summarized in Table 9. Table 7

It is evident that formulations C11 and C13 containing an anionic polymer (Dequest P9030) provide better cleaning of SiN surfaces. However, it is evident from Table 8 that the anionic polymer is ineffective for cleaning unsurface-modified silica particles from the tungsten surface. However, formulation C13 comprising anionic polymers and polymers containing polyethylene glycol groups provided excellent cleaning results for all surfaces involving TEOS, SiN and tungsten. The results also show a significant improvement in defect count for the formulations of the present invention relative to the 2% ammonia solution commonly used in the industry for post-CMP cleaning. Example 6

The recipes listed in Table 7 were used to clean TEOS wafers previously measured for defect count using the KLA Surfscan SP2. Pass the wafer through the Ontrak brush box cleaner. Only use the second brush box for cleaning. In this second brush box, the formula was dispensed for 30 seconds without a rinsing step in the brush box. The wafer is then sent to a spin-rinse dry station for drying. Defect counts on TEOS wafers were measured after this treatment. An increase in the number of defects after treatment (defect adder) indicates defects resulting from incomplete rinsing of the cleaning chemistry. It is highly desirable that the cleaning chemistry be easy to rinse off with minimal increase in the number of imperfections due to incomplete rinsing. Table 8

儘管本發明已經聯合本發明的特定具體實例加以描述，但是很明顯地按照前面的描述此領域之習知技藝者將顯而易見許多替代物、修飾及變化。 因此，可偏離這些細節而不悖離總體發明概念的精神或範疇。Table 8 shows the number of defect increases for different chemistries. It is apparent that the chemistry of the non-ionic polymers containing ethylene oxide (C12 and C13) has the lowest number of defect increases, indicating that the cleaning chemistry can be easily washed off the surface, which is important for increasing the cleaning process window. Example 7 The ability to remove small particles from TEOS surfaces was evaluated by drop drying of a slurry containing about 20% Fuso PL-3 particles on TEOS wafer coupons. Formula C1 of Table 2 was diluted with water and 40% ammonium fluoride as described in Table 9. The wafer coupons with the dry slurry were immersed in the cleaning solution for 15 minutes with agitation. After 156 minutes, the sample was rinsed and dried. The samples were examined under a scanning electron microscope to determine the removal of silica particle residues. The formula without ammonium fluoride (D9) showed little removal of dry silica residue, while the formula containing ammonium fluoride (D8) showed a substantial reduction in the removal of silica residue. This means that the addition of ammonium fluoride helps to remove the silicon oxide residues. Table 9

Although the present invention has been described in conjunction with specific embodiments of the invention, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, departures from these details may be made without departing from the spirit or scope of the general inventive concept.

Figure 1 shows polarization diagrams providing passivation current densities tested at 0.2 wt% concentration for various chemistries.

Claims (20)

A chemical mechanical planarization (CMP) post-cleaning composition, comprising: at least one organic acid or a salt thereof selected from the group consisting of dicarboxylic acid, hydroxycarboxylic acid, polycarboxylic acid, salts thereof, and combinations thereof ; fluoride, which is selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium bifluoride, quaternary ammonium fluoride and combinations thereof; at least one polymer additive, which is selected from acrylic acid-acrylamido propane Sulfonic acid copolymer and its salt, poly(2-acrylamido-2-methyl-1-propanesulfonic acid) and its salt, carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose , poly(1-vinylpyrrolidone-2-dimethylaminoethyl methacrylate) copolymer, poly(4-styrene sulfonate sodium), polymers containing propylene oxide, poly(4-styrene sulfonate) acid) and salts thereof, polypropylene glycol, polyacrylamide, poly(acrylamide/acrylic acid) copolymers and salts thereof, and the group consisting of combinations thereof; and water; wherein the composition has between 1 and less than pH between 5 and the composition does not contain alkyl, aryl or aralkyl substituted ammonium hydroxide. The post-CMP cleaning composition of claim 1, further comprising at least one component selected from the group consisting of: a surfactant, which is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants The group consisting of surfactants, amphoteric surfactants, and mixtures thereof; corrosion inhibitors; biological preservatives; and pH adjusters. The post-CMP cleaning composition of claim 1, wherein the at least one polymer additive has a molecular weight ranging from 100 to 1,000,000. The post-CMP cleaning composition of claim 1, wherein the at least one organic acid or its salt is 1 to 30 wt %, the at least one polymer additive is 0.1 to 3 wt %, the fluoride intermediate At 1 to 25 wt%, and the balance water. The post-CMP cleaning composition of claim 4 further comprises deionized water 2 to 500 times its volume. The post-CMP cleaning composition of claim 1, wherein the at least one organic acid or its salt is selected from the group consisting of hydroxycarboxylic acid or its salt, dicarboxylic acid or its salt, and combinations thereof. The post-CMP cleaning composition of claim 1, wherein the at least one organic acid or a salt thereof is selected from the group consisting of oxalic acid, citric acid, malonic acid or a salt thereof and a combination thereof; the at least one polymer The additive is the propylene oxide containing polymer. The post-CMP cleaning composition of claim 1, wherein the post-CMP cleaning composition comprises 0.5 to 5 wt % of oxalic acid or its salt, 0.5 to 5 wt % of citric acid or its salt, 0.5 to 5 wt % malonic acid or a salt thereof; and 0.1 to 2% by weight of at least one polymer additive selected from the group consisting of acrylic acid-acrylamidopropane sulfonic acid copolymer, polypropylene glycol, and combinations thereof; and 1 to 25% by weight of fluoride. As claimed in claim 1, the post-CMP cleaning composition, wherein the post-CMP cleaning composition comprises 1 to 30% by weight of citric acid or a salt thereof; 0.1 to 3% by weight of at least one polymer additive, which is selected from the group consisting of acrylic acid-acrylamidopropane sulfonic acid copolymer, polypropylene glycol, and combinations thereof; and 1 to 25 weight percent fluoride. The post-CMP cleaning composition as claimed in claim 1, wherein the post-CMP cleaning composition comprises 0.0001 wt % to 10 wt % of a surfactant; wherein the surfactant is in the conductivity

The composition at 40 mS/cm was stable without any haze or precipitation. The post-CMP cleaning composition of claim 10, wherein the surfactant comprises at least dinegatively charged anionic groups. As claimed in claim 2, the post-CMP cleaning composition, wherein the surfactant is a diphenyl ether disulfonic acid or a salt thereof having the following structure:

wherein R is selected from H or a linear or branched alkyl having a carbon chain length between 1 and 20. A method of cleaning a semiconductor wafer after chemical mechanical planarization (CMP), the semiconductor wafer comprising at least one surface selected from the group consisting of metal films, dielectric films, and combinations thereof, the method comprising: providing the semiconductor wafer circle; providing the aforementioned post-chemical mechanical planarization (CMP) cleaning composition of any one of claims 1 to 12; and cleaning the semiconductor wafer using the post-CMP cleaning composition. The post-CMP cleaning method of claim 13, wherein the metal film is selected from the group consisting of copper, tungsten, cobalt, aluminum, titanium, ruthenium, alloys thereof, and combinations thereof; the dielectric film is selected from Silicon oxide films derived from tetraethyl orthosilicate (TEOS) precursors, dielectric films having at least one element selected from the group consisting of silicon, carbon, nitrogen, oxygen, and hydrogen, and the group consisting of combinations thereof Group. As claimed in claim 13, the post-CMP cleaning method, wherein the post-CMP cleaning method is selected from brush box cleaning, spray cleaning, ultrasonic cleaning, and pad polishing A group consisting of buff cleaning on a pad, single wafer spray tools, batch immersion cleaning tools, and combinations thereof. As claimed in claim 13, the post-CMP cleaning method, wherein the post-CMP cleaning composition comprises 1 to 30 wt % of at least one organic acid or salt thereof, 0.1 to 3 wt % of at least one polymer additive, 1 to 30 wt % 25 wt% fluoride, and the balance water, the at least one polymer additive has a molecular weight range between 100 and 1,000,000; the post-CMP cleaning composition is optionally diluted with deionized water at the point of use 2 to 500 times; and the diluted CMP cleaning composition etches the dielectric film at an etch rate between 0.2 and 50 angstroms/min; etches tungsten at an etch rate of less than 1 angstrom/min; and at room temperature and the at least one surface includes at least one of SiO ₂ , W, Ti, TiN and SiN films. A system for cleaning a semiconductor wafer after chemical mechanical planarization (CMP), the semiconductor wafer comprising at least one surface selected from the group consisting of metal films, dielectric films, and combinations thereof, the system comprising: the semiconductor wafer ; and the aforementioned post-chemical mechanical planarization (CMP) cleaning composition of any one of claims 1 to 12; wherein the at least one surface is in contact with the post-CMP cleaning composition. The post-CMP cleaning system of claim 17, wherein the metal film is selected from the group consisting of copper, tungsten, cobalt, aluminum, titanium, iron, ruthenium, alloys thereof, and combinations thereof; the dielectric film is Consists of silicon oxide films derived from tetraethyl orthosilicate (TEOS) precursors, dielectric films having at least one element selected from the group consisting of silicon, carbon, nitrogen, oxygen, and hydrogen, and combinations thereof 's group. The post-CMP cleaning system of claim 17, wherein the system is used for a cleaning system selected from the group consisting of brush box cleaning, spray cleaning, ultrasonic cleaning, polishing on pad cleaning, single-wafer spray tools, batch immersion cleaning tools, and combinations thereof One of the cleaning methods in the group. The post-CMP cleaning system of claim 17, wherein the post-CMP cleaning composition comprises 1 to 30 wt% of at least one organic acid or salt thereof, 0.1 to 3 wt% of at least one polymer additive, 1 to 30 wt% 25 wt% fluoride, and the balance water, the at least one polymer additive has a molecular weight range between 100 and 1,000,000; when the post-CMP cleaning composition is diluted 2 to 500 with deionized water at the point of use times; the diluted CMP cleaning composition etched the dielectric film at an etch rate between 0.2 and 50 angstroms/min; etched tungsten at an etch rate of less than 1 angstrom/min; and at room temperature with an etch rate of less than The titanium nitride film is etched at an etch rate of 5 angstroms/min; and the at least one surface includes at least one of SiO ₂ , W, Ti, TiN and SiN films.

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